Process for the production of novel cyclopentenylcyclopentenyl ethers



United States Patent 3,235,606 PROCESS FOR THE PRODUCTION 6F NOVEL CYCLOPENTENYLCYCLDPENTENYL ETHERS Erich Marcus and John T. Fitzpatrick, CharlestomW. Va.,

assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed July 6, 1961, Ser. No. 122,067

7 Claims. (Cl. 260-611) Tinsley et al., and now abandoned. One isomeric form of said cyclo-pentenylcyclopentenyl halides can be represented by the following formula:

where R represents hydrogen or an alkyl group of from 1 to 8 carbon atoms and X represents chlorine or bromine.

The cyclopentenylcyclopentenyl halides can be prepared by reacting a halocyclopentene of the formula:

with a cyclopentadiene of the formula:

wherein X and R have the same meaning as previously set forth in the presence of a Friedel-Crafts catalyst.

Examples of cyclopentenylcyclopentenyl halides which are useful in the novel process of this invention include cyclopentenylcyclopentenyl chloride, cyclopentenylcyclopentenyl bromide, methylcyclopentenylethylcyclopentenyl chloride, butylcyclopentenylbutylcyclopentenyl bromide, etc. It is to be pointed out that the number and position of the alkyl group of the cyclopentenyl ring is far from being critical and every combination as well as mixtures is contemplated herein.

The monoepoxides which can be used in the novel process of this invention can be represented by the following general formula:

wherein R individually represents hydrogen, alkyl groups of from 18 carbon atoms, haloalkyl groups wherein the alkyl group has from 18 carbon atoms, vinyl and phenyl; R individually represents hydrogen, R and R taken together may represent alkylene groups such as trimethylene or tetramethylene. Illustrative of the epoxides which can be used in the novel process of this invention are ethylene oxide, propylene oxide, styrene P ICC oxide, epichlorohydrin, butadiene monoxide, cyclohexene oxide and cyclopentene oxide.

As has heretofore been pointed out, the novel process of our invention is carried out by reacting a monoepoxide with a cyclopentenylcyclopentenyl halide in the presence of a Friedel-Cratfts catalyst. As examples of Friedel- Crafts catalysts which are operable, one can include zinc chloride, mercuric chloride, zinc bromide, stannic chloride, aluminum chloride and boron trifiuoride. The preferred catalyst is zinc chloride. The amount of catalyst employed is not narrowly critical and can vary over a Wide range. Catalyst concentrations as low as 0.01 of a percent to as high as 10 percent by weight based on the amount of cyclopentenylcyclopentenyl halide are operable. However, it is preferred to employ 0.05 to 2 percent by weight based on the Weight of cyclopentenylcyclopentenyl halide.

The temperature at which the process is carried out is also not narrowly critical and temperatures of from to +80 C. are operable. However, it is preferred to conduct the process at temperatures in the range of 40 to +40 C.

The molar ratio of the epoxide to the cyclopentenylcyclopentenyl halide is fiar from being critical and an excess of either can be employed. For economical considerations, it is prefer-red to employ a 1:1 molar ratio.

The order of addition of reactants is also not critical and is a matter of choice but it is preferred to gradually add one reactant to the other since the progress of the reaction can be better controlled. It is also pointed out that a solvent is not necessary, although any sol-vent which is inert -t othe reactants and reaction product under the conditions specified can be employed. Examples of such solvents include petroleum ether, ethyl ether, chloroform, benzene and ethyl acetate.

In another aspect, this invention relates to novel cyclopentenylcyclopentenyl ethers which are products resulting from the novel process of this invention. At the outset, it is pointed out that the novel cyclopentenylcyclopentenyl ethers are mixtures of various isomeric forms, the complete nature of which, or the distribution of which, in the product has not been completely determined.

In order to aid in understanding the various products which can result from the novel process Of this invention, the following formulas are presented:

F 1 R2 R: l meat...

wherein R represents hydrogen and an alkyl of from 1-8 carbon atoms; R individually represents hydro-gen, an alkyl of from 1-8 carbon atoms and haloalkyl groups of from l-8 carbon atoms; R individually represents hydrogen; R and R taken together represent alkylene groups such as trimethylene and tetra methylene; R represents vinyl or phenyl; and X rep-resents chlorine or bromine.

It is to be understood that the above formulas are intended to represent the main isomeric products resulting from the novel process of this invention.

The isolation of the various mixtures of the cyclopentenylcylopentyl ethers from the reaction mixture can be accomplished in a variety of ways. The catalyst can be removed by washing the reaction mixture with water. Alternatively, the reaction product may be subjected to vacuum distillation without washing. It is to be pointed out that the reaction mixture can be used per se without any isolation.

The novel cyclopentenylcyclopentenyl ethers of this invention are useful in the same manner as ordinary, simple ethers. Thus, they can be used as solvents, paint thinners and as intermediates for the preparation of a wide variety of compounds containing cyclopentenyl rings. It is to be pointed out that the utility of these ethers applies to the isometric mixtures as well as the pure compound.

The following example will illustrate the novel process of this invention.

Di(cyclpentenyl) Z-chloroethyl ether Cyclopentadiene (528 grams, 8.0 mols) was added during a period of two hours with stirring to a mixture of 3-chlorocyclopentene (820 grams, 8.0 mols) and pulverized zinc chloride (0.8 gram), while the temperature was maintained at 0 C. The mixture was stirred for an additional two hours at 0 C. The crude cyclopentylchlorocyclopentene was used for the further reaction with ethylene oxide in this form.

Ethylene oxide (352 grams, 8.0 mols) was added during a period of one hour with stirring to the crude cyclopentenylchlorocyclopentene while the temperature was maintained at 0 C. The mixture was stirred for an additional hour at the same temperature. After addition of petroleum ether (B.P 3537, 500 ml.), the reaction product was washed with water, dried over calcium chloride, and distilled through a long column packed with glass helices. The following fractions were obtained after removal of solvent.

Fraction 13.1. in Pressure Weight Yield in 11 20/1) (14 C. in mm. in Grams percent 1 76-102 1. 0-0. 6 33 2 2 102-110 0. 9 35 2 3 110-117 0. 9 1071 1. 5034 l. 058 4 150-160 0. 148 b o b 5 160-175 0.15-(17 9r 9 i Residue 80 Distilled without rectification. b Fractions 4 and 5 combined.

Fraction 3 analyzed as follows:

ANALYSIS FOR CmHl'IOCl G H Cl M Calculated 67. 76 8. 00 16. 71 58. 80 Found 67. 37 8. 09 16. 87 58. 9

What is claimed is:

1. The process for the production of cyclopentenylcyclopentenyl ethers which comprises reacting a cyclopentenylcyclopentenyl halide, one isomeric form of said halide corresponding to the formula:

wherein R is selected from the group consisting of hydrogen and alkyl groups of from 1-8 carbon atoms and X is selected from the group consisting of chlorine and bromine with a monoepoxide of the formula:

sc cr.

Till

wherein R is selected from the group consisting of hydrogen and alkyl groups of from 1 to 8 carbon atoms and wherein X is selected from the group consisting of chlorine and bromine; and a 1,2-ethoxyalkane having up to 10 carbon atoms; in the presence of a Friedel-Crafts catalyst; at a temperature of from to +80 C.

3. A process for the production of cyclopentenylcyclopentenyl ethers which comprises contacting a cyclopentenylcyclopentenyl halide, one isomeric form of said halide corresponding to the formula:

wherein R is selected from the group consisting of hydrogen and alkyl groups of from 1 to 8 carbon atoms and wherein X is selected from the group consisting of chlorine and bromine; and a halo-1,2-epoxyalkane having up to 10 carbon atoms; in the presence of a Friedel-Crafts catalyst; at a temperature of from -80 to +80 C.

4. A process for the production of cyclopentenylcyclopentenyl ethers which comprises contacting a cyclopentenylcyclopentenyl halide, one isomeric :form of said halide corresponding to the formula:

wherein R is selected from the group consisting of hydrogen and alkyl groups of from 1 to 8 carbon atoms and wherein X is selected from the group of chlorine and bromine; and ethylene oxide at a temperature of from -80 C. to +80 C., in the presence of from 0.1 to 10 percent by weight of a Friedel-Crafts catalyst.

5. A process for the production of cyclopentenylcyclopentyl ethers which comprises contacting a cyclopentenylcyclopentenyl halide, one isomeric form of said halide corresponding to the formula:

wherein R is selected from the group consisting of hydrogen and alkyl groups of from 1 to 8 carbon atoms and wherein X is selected from the group of chlorine and bromine; and propylene oxide at a temperature of from 80 C. to +80 C., in the presence of from 0.1 to 10 percent by weight of a Friedel-Crafts catalyst.

6. A process for the production of cyclopentenylcyclopentyl ethers which comprises contacting a 5 6 cyclopentenylcyclopentenyl halide, one isomeric form References Cited by the Examiner of said halide corresponding to the formula: UNITED STATES PATENTS 2,608,586 8/1952 Ballard et al 260614 5 FOREIGN PATENTS I 1 l 473,997 5/1951 Canada.

672,416 5/1952 Great Britain.

10 OTHER REFERENCES wherein R is selected from the group consisting of hy- Bedos, Compt. Rend. (1926), vol. 183, pp. 562-565. drogen and alkyl groups of from 1 to 8 carbon atoms Thomas, Anhydrous Aluminum Chloride in Organic and wherein X is selected from the group of chlorine and Chemistry (1941), page 769.

bromine; and styrene oxide at a temperature of from 80 C. to +80 C., in the presence of from 0.1 to 10 15 LEON ZITVER, Primary Examiner.

percent by weight of a Friedel-Crafts catalyst. LES B AR ER E 7. Di(cyclopentenyl) 2-chloroethyl ether. CHAR P K xammer 

1. THE PROCESS FOR THE PRODUCTION OF CYCLOPENTENYLCYCLOPENTENYL ETHERS WHICH COMPRISES REACTING A CYCLOPENTENYLCYCLOPENTENYL HALIDE, ONE ISOMERIC FORM OF SAID HALIDE CORESPONDING TO THE FORMULA: 